Journal of Molecular Structure 1250 (2022) 131778

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstr

Rosin imidazoline as an eco-friendly corrosion inhibitor for the carbon

steel in CO2 -containing solution and its synergistic effect with
thiourea
Shuai Geng a, Junying Hu a,∗, Jiansheng Yu b, Chenfeng Zhang a, Heng Wang a,
Xiankang Zhong a,b,∗
a
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, Sichuan 610500, China
b
Environmental Protection and Quality Supervision and Inspection, Chuanqing Drilling Engineering Co., Ltd., Research Institute of Safety, Guanghan, Sichuan
618300, China

a r t i c l e i n f o a b s t r a c t

Article history: Rosin is known as an eco-friendly raw material from natural plants. The main component of rosin is
Received 1 August 2021 abietic acid. Abietic acid has a carboxyl and a tricyclic phenanthrene skeleton in which conjugated dou-
Revised 11 October 2021
ble bonds are present. Conjugation structure will lead to local enrichment of electrons, thereby creating
Accepted 18 October 2021
sites that can be used for adsorption. In this case, it is expected that a better performance could be ob-
Available online 21 October 2021
tained if an inhibitor is synthesized from rosin. In this work, rosin was used to synthesize an imidazoline
Keywords: derivative as a corrosion inhibitor, then the corrosion inhibition performance and synergistic effect with
Rosin thiourea (TU) of rosin imidazoline (RI) for carbon steel in test solution were studied using weight loss
Carbon steel measurement, electrochemical techniques and surface characterization. The results show that the inhibi-
Corrosion inhibitor tion efficiency of RI reaches 83.8% at 200 mg/L. A further increase in RI concentration does not effectively
DFT improve the inhibition performance since the critical micelle concentration of RI is present at around
200 mg/L. The molecular characteristics of RI was analyzed by quantum chemical calculations. It clearly
shows that multiple adsorption sites exists in the RI molecular structure, hence RI could offer a good
inhibition performance. With the compounding of 200 mg/L RI and 10 mg/L TU, the inhibition efficiency
could increase as high as 89.8%, demonstrating a good synergistic effect between RI and TU. The corre-
sponding synergistic mechanisms are also proposed.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction is the one of the most cost effective and simple operational ways
[8–11].
CO2 corrosion is one of the main causes for the failure of In general, organic molecules containing heteroatoms (such as
oil and gas pipelines, which results in serious security risk and N, S, O) can strongly adsorb on the metal surface owing to their
huge economic loss [1–4]. It is well known that the dissolved CO2 lone electron pair or π -electron structure, showing excellent cor-
reacts with H2 O to form H2 CO3 , which then dissociates to H+ , rosion inhibition performances [12–14]. However, the usage is lim-
2−
HCO− 3 and CO3 , hence a drop in solution pH [5]. This means that ited because of the environmental risks of some organic inhibitors.
serious corrosion of pipelines could occur in the CO2 -containing At present, imidazoline and its derivatives are widely used in oil
environment. In petroleum industry, a large amount of low car- and gas field due to their excellent corrosion inhibition perfor-
bon steels have been applied due to the cost considerations [6]. mance and biodegradation characteristics [15,16]. Based on the
Unfortunately, low carbon steels are very easily corroded in CO2 previous work, it is believed that the corrosion inhibition mech-
containing-environment [7]. Although there are many ways to in- anism of imidazoline derivatives can be attributed to the inhibitor
hibit or prevent CO2 corrosion, the addition of corrosion inhibitors films which act as barriers to prevent metal from the attack of the
corrosive species [17]. Considering the availability of raw materi-
als and economic cost, most imidazoline corrosion inhibitors are
∗
Corresponding authors at: State Key Laboratory of Oil and Gas Reservoir Ge- usually synthesized with fatty acids and polyamine [18–21]. Those
ology and Exploitation, Southwest Petroleum University, Chengdu 610500, Sichuan, imidazoline inhibitors typically contain only one imidazoline ring
China.
and thus only one adsorption site exists. The corrosion inhibition
E-mail addresses: [email protected] (J. Hu), [email protected] (X.
Zhong). performance of imidazoline derivatives depends largely on its ad-

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0022-2860/© 2021 Elsevier B.V. All rights reserved.
S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

sorption capacity [22]. Accordingly, the performance of the imida- Table 1

Components of test solution (g/L).
zoline corrosion inhibitor with a single adsorption site is limited.
Previous studies have shown that an increase in the number of NaCl CaCl2 MgCl2 Na2 SO4 NaHCO3
imidazoline rings can increase adsorption sites, thereby improving 20.57 1.34 0.31 0.04 1.11
the inhibition performance of inhibitors [23]. Therefore, the per-
formance of corrosion inhibitor can improve by change the alkyl
form from the perspective of molecule structure. it is also possible
to improve the corrosion inhibition performance by changing side concentrated ammonia as eluant. Then, FT-IR spectroscopy (WQF-
chain from a straight chain to a ring structure which contains a 520, Beijing Rayleigh analytical instrument, China), 1 H NMR mea-
conjugated structure to increase adsorption sites. surements (Bruker 400 NMR Spectrometer, Switzerland) and HRMS
Rosin is a resin which can be extracted from the pine tree. The (Xevo G2-XS QTof, Waters Corporation, USA) were employed to de-
main component of rosin is abietic acid. Abietic acid has a carboxyl termine the molecular structure of RI.
and a tricyclic phenanthrene skeleton in which conjugated dou-
ble bonds are present [24]. The structural characteristics of rosin 2.2. Materials and solutions
make it a suitable material for the synthesis of excellent imida-
zoline corrosion inhibitor. Conjugation structure will lead to local The material used for this work was carbon steel with the com-
enrichment of electrons, thereby creating sites that can be used position (wt.%) of C (0.19%), Si (0.25%), Mn (0.52%), S (0.015%), C
for adsorption. In this case, it is expected that a better perfor- (0.25%), Ni (0.30%), Cu (0.25%), P (0.005%) and balance Fe. The
mance could be obtained if an inhibitor is synthesized from rosin. specimen with dimensions of 40.0 mm × 12.7 mm × 2.6 mm
At the same time, the advantages of low price and environmentally was machined for the weight loss measurement. For electrochemi-
friendly properties of rosin can meet the requirements of indus- cal measurements, a cylindrical specimen was used as the working
trial production and environmental protection. In previous reports, electrode (WE). Details about the WE are described elsewhere [30].
Okafor et al. [25] and Liu et al. [26] used rosin and diethylene- For each test, specimens were grounded in turn by 80 0, 120 0 and
triamine to synthesize an imidazoline derivatives. However, their 1500 grit SiC paper, then degreased with isopropanol, rinsed with
studies about the corrosion inhibition mechanism of rosin imida- ethanol. Before the experiment, the outer diameter and height of
zoline only focused on the role of the imidazoline ring, the effect the ring specimen were measured to calculate the exposed area.
of tricyclic phenanthrene skeleton on corrosion inhibition was ne- The composition of the test solution is listed in Table 1. Prior to
glected. the test, solutions were de-aerated by purging CO2 for 2 h. During
In this work, rosin was used as raw material to synthesize an the measurement, the temperature of the solution was maintained
imidazoline derivative with tetraethylenepentamine. The corrosion at 80 °C, and CO2 was continuously purging to keep the solution
inhibition performance of RI was assessed by weight loss and elec- saturated with CO2 .
trochemical measurement in CO2 -containing solution at 80 °C. The
surface characteristics of the samples were studied by scanning
electron microscopy (SEM) and X-ray photoelectron spectroscopy 2.3. Surface tension measurements
(XPS). At the same time, the adsorption model of the inhibitor
molecule was also determined by isothermal adsorption curve. To study the surface activity of RI, the surface tension of so-
Quantum chemistry calculations provides more information about lutions was measured using drop shape analyzer (KRUSS DSA30S,
RI molecules, including molecular orbital distribution, molecular Hamburg, Germany) at room temperature. Further, the critical mi-
electrostatic potential, and condensed Fukui function. In addition, celle concentration (CMC) was obtained by plotting the surface
the previous studies have shown that corrosion inhibitors can work tension of solutions against RI concentrations.
synergistically with other substances such as mercaptoethanol and
thiourea to increase the inhibition efficiency [27,28]. Thus, thiourea
2.4. Weight loss measurement
was added to work together with RI as a compound inhibitor to
further improve the inhibition performance of RI in this work.
Before and after the experiment, the samples were weighed us-
ing an electronic balance with an accuracy of 0.1 mg. After 168 h
2. Experimental and quantum chemical calculations
immersion, the corrosion products on the sample surface were re-
moved by chemical cleaning. The solution for chemical cleaning
2.1. Synthesis and molecular structure characterization of RI
consisted of 10 g hexamethylenetetramine, 100 mL concentrated
hydrochloric acid and 900 mL deionized water.
RI was synthesized according to the route shown in Fig. 1. Rosin
The corrosion rate (v, mm/a) was calculated according to
was purchased from Macklin (Shanghai, China). Tetraethylenepen-
Eq. (1) [31]:
tamine and xylene were purchased from Chengdu Kelon Chemi-
cal Reagent Company (Chengdu, China). Under nitrogen, the mix- 87600m
ν= (1)
ture of rosin (30.2 g, 0.1 mol) and xylene (45 ml) placed in a ρ At
four-necked round-bottomed flask was heated with stirring by a
magnetic stirring bar. When temperature reached 120 °C, 22.7 g where m (g) is the weight loss of the carbon steel sample before
(0.12 mol) tetraethylenepentamine was added slowly through a and after soaking in the test solution, ρ (g/cm3 ) is the density of
pressure-equalizing addition funnel. After the addition, the mixture carbon steel samples, A (cm2 ) is the surface area of specimen, and
was kept at 120 °C for 4 h. Then the temperature was slowly in- t (h) is the experiment duration.
creased to 220 °C for 6 h. After cooling to room temperature, the The inhibition efficiency (η) based on weight loss measurement
mixture was preliminarily purified by liquid-liquid extraction using result can be described by Eq. (2) [32]:
CH2 Cl2 : saturated NaCl (1:1, v/v) [29]. Then, the primarily purified ν0 − ν1
products could be used for weight loss and electrochemical mea- η= × 100% (2)
ν0
surements. To determine the molecular structure, the preliminarily
purified product was further purified in a chromatographic column where ν0 and ν1 are the corrosion rate of steel samples in the ab-
of neutral alumina using CH2 Cl2 : MeOH (8:2, v/v) with one drop of sence and presence of inhibitor, respectively.

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S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

Fig. 1. Synthetic routes of RI.

2.5. Electrochemical measurements

Electrochemical impedance spectroscopy (EIS) and polariza-

tion curves were measured using an electrochemical workstation
(CS310H system, Wuhan Corrtest instruments Corp. Ltd, Wuhan,
China). A classic three-electrode system was used, where the car-
bon steel sample was used as WE, Pt plates served as counter elec-
trodes and the reference electrode was Ag/AgCl electrode.
After 1 h immersion, the EIS measurement was conducted at
the open circuit potential (OCP) with the amplitude of 5 mV in
the range of 100 kHz to 0.01 Hz. Subsequently, the polarization
curve was measured. The polarization curves were measured from
−0.25 V to +0.25 V vs. OCP, and the scanning rate is 1 mV/s. The
EIS parameters were obtained by fitting the data with an equiva-
lent circuit using ZSimpWin software. The polarization curves were
processed by the Tafel extrapolation method.

2.6. Surface analysis

All specimens used for surface analysis were also immersed Fig. 2. FT-IR spectrum of the RI.
into the solution along with the weight loss measurement. Af-
ter 168 h immersion, the samples were taken out then dried
in the N2 gas flow. The surface and cross-sectional morpholo- trophilic regions can be recognized within the RI molecule. To bet-
gies of the sample were observed using a scanning electron mi- ter display the data, the Multiwfn program was used to process
croscopy (SEM) (Zeiss Evo 50 XVP, Jena, Germany). X-ray photo- the data, and the VMD program was used to display the molecu-
electron spectroscopy (XPS) (ESCLAB Xi+ , Thermo Fisher Scientific, lar orbitals and Fukui function calculations data using the drawing
Waltham, America) was used to analyze the composition of the method of the combination of isosurface and space-filling model
surface layer formed on samples. The obtained XPS high-resolution [34,35].
spectra were analyzed using XPSPEAK 4.1 software. Fukui function was calculated by according to Formulas (3) and
(4) [36]:
2.7. Quantum chemical calculations for nucleophilic reaction fi+ = qi (N + 1 ) − qi (N ) (3)

The molecular parameters of RI in protonated and solvated

phases were calculated by density functional theory. The molec- for electrophilic reaction fi− = qi (N ) − qi (N − 1 ) (4)
ular structure of RI was optimized by b3lyp/6-311 G (d, p) method where qi (N + 1 ), qi (N ) and qi (N − 1 ) are the net charge of atom i
using Guassian 09 W, which is a reliable method to calculate in cathodic, neutral and anodic systems, respectively.
quantum chemical parameters [33]. Based on the above calcula-
tions, the highest occupied molecular orbitals (HOMO) and HOMO- 3. Results and discussion
1, the lowest unoccupied molecular orbitals (LUMO) and LUMO+1
and molecular electrostatic potential of the molecule could be ob- 3.1. Molecular structure characterization of RI
tained. Simultaneously, the condensed Fukui function was also cal-
culated. Condensed Fukui function can clearly reflects the reactiv- Fig. 2 shows the FT-IR spectrum of RI. The broad bands around
ity of the atoms in the RI molecule, so the nucleophilic and elec- 3288 cm−1 are attributed to vibration of -N-H. The peaks at

3
S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

1
Fig. 3. H NMR spectrum of the RI.

Fig. 4. Mass spectrum of the RI.

Fig. 5. Surface tension vs. RI concentration plot.

Table 2
Weight loss measurements results of carbon steel in test so-
lution with different concentrations of RI/TU after 168 h.

RI/TU Concentration(mg/L) v±SD /(mm•a−1 ) η/% C=N bond, which directly indicates the existence of imidazoline
ring structure [37,38].
Blank 0.2287 ± 0.0117 —
50/0 0.0612 ± 0.0058 73.2
The spectrum of 1 H NMR is shown in Fig. 3. 1 H NMR (400 MHz,
100/0 0.0521 ± 0.0024 77.2 Chloroform-d) for RI: δ 5.73 (s, 1H, C=CH–C), 5.31 (s, 1H, C=CH–C),
200/0 0.0370 ± 0.0045 83.8 4.90 (dt, J = 30.9, 9.8 Hz, 1H, -N-CH2– C), 3.76 (s, 1H, -CH2– N-),
400/0 0.0215 ± 0.0023 90.6 3.73–3.59 (m, 5H, -CH2 –N=), 3.43 – 3.22 (m, 7H, -CH2– N-), 2.92–
200/10 0.0233 ± 0.0050 89.8
2.65 (m, 10H, -CH2 -), 2.54 – 2.38 (m, 7H, -CH2 -), 2.20 (p, J = 7.0 Hz,
200/20 0.0236 ± 0.0060 89.7
200/40 0.0274 ± 0.0005 88.0 2H, -CH), 2.06 (s, 2H, -CH2 -), 2.02–1.93 (m, 3H, -CH2 -/ -CH), 1.91
200/80 0.0303 ± 0.0012 86.8 (s, 2H, -CH), 1.86 (d, J = 12.5 Hz, 3H, -CH), 1.53–1.35 (m, Hz, 8H,
-CH2 -), 1.24–1.09 (m, 17H, -CH2 -/ -NH1 -), 1.05–0.95 (m, 8H, -CH3 /-
CH2 -), 0.95–0.73 (m, 9H, -CH3 ).
The results of FT-IR and 1 H NMR spectra indicate that the target
2929 cm−1 and 2866 cm−1 correspond to the asymmetric and product was successfully obtained in this work. In addition, we car-
symmetric stretching vibration of -CH2 -, respectively. And the peak ried out mass spectrometry of RI, which also confirmed this con-
around 1633 cm−1 is caused by the stretching vibration of the - clusion, and obtained data display in Fig. 4.

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S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

Fig. 6. Nyquist plots of specimens in test solution with different concentrations of inhibitors at 80 °C and the equivalent circuit used to fit the obtained impedance spectra.

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S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

Table 3
Fitted parameters of the EIS for carbon steel test solution with different concentration of RI/TU at 80 °C.

RI/TU Concentration (mg/L) Rs (•cm2 ) Y01 (×10−4 −1 •cm−2 •s−n ) n1 Rf (•cm2 ) Y02 (×10−4 −1 •cm−2 •s−n ) n2 Rct (•cm2 ) ηE %
Blank 9.76 1.943 1.00 15.53 7.158 0.77 67.5 —
50/0 8.62 0.227 1.00 15.18 2.120 0.64 463.3 85.4
100/0 12.50 1.344 0.69 18.00 1.000 0.59 1401.1 95.2
200/0 25.03 0.060 1.00 17.57 0.415 0.79 3654.0 98.2
400/0 10.18 0.011 1.00 23.59 0.995 0.65 10,260.2 99.3
200/10 44.00 0.424 0.80 — — — 8800.0 99.2
200/20 49.16 0.374 0.76 — — — 14,000.0 99.5
200/40 91.53 0.415 0.73 — — — 18,530.0 99.6
200/80 107.10 0.385 0.75 — — — 20,530.0 99.7

Imidazoline is an organic substance with amphiphilic structure,

it shows the characteristics of surfactant. Surfactant is character-
ized by the ability to adsorb on the metal surface, reducing the free
energy of the system. This imply imidazoline as corrosion inhibitor
can form a highly ordered molecular film at the metal/solution in-
terface to isolate the steel surface from the aggressive media [40].
According to the theory of CMC, when the dissolution of surfac-
tant in solution reaches CMC, a further increase in the concentra-
tion of surfactant does not increase the adsorption amount on the
surface, suggesting that beyond CMC, the performance of corrosion
inhibitor will not be further improved [41]. The CMC of RI, around
200 mg/L shown in Fig. 5, can also be verified by the corrosion
evaluation results in the following sections.

3.3. Weight loss measurements

The weight loss results of specimen in blank solution and so-

lutions with different concentrations of RI are listed in Table 2.
It can be found that without inhibitor, the corrosion rate of the
specimen is as high as 0.2287 mm/a, meaning a server corrosion
has occurred in this environment. In the presence of RI, the corro-
sion rate decreases greatly. At 200 mg/ L and 400 mg/L, the corro-
sion rate is 0.0370 mm/a and 0.0215 mm/a, respectively. The corre-
sponding corrosion inhibition efficiencies are 83.8% and 90.6%. Ac-
cording to the NACE standard RP0775-2005 [42], the above corro-
sion rates could be accepted in the oil field. However, a further
increase in concentration from 200 to 400 mg/ L shows negligi-
ble effect on reduction of corrosion rate. The reason for this phe-
nomenon is that when the concentration exceeds the CMC of RI,
the adsorption of RI on the metal surface reaches saturation, which
makes it difficult to further improve the integrity of adsorption
film. This meaning that when concentration exceeds 200 mg/L, a
further increase in RI concentration does not effectively help to im-
prove the inhibition performance.
To further improve the corrosion inhibition performance, TU
was used to work together with RI to creak a compound inhibitor.
TU has been used in commercial corrosion inhibitor formulations
due to its strong interfacial adsorption properties. TU with dif-
Fig. 7. The polarization curves of specimen in test solution with different concen- ferent concentrations was added to the solution which contains
trations of inhibitors at 80 °C. 200 mg/ L RI. It can be found that with the addition of TU, the
corrosion rate decreases significantly compared with its absence,
and the corrosion inhibition efficiency further improved. When the
3.2. Surface tension of the RI-containing solution concentration of RI is 200 mg/L and the concentration of thiourea
is 10 mg/L, the corrosion rate decreased to 0.0233 mm/a, which is
It can be seen from Fig. 5 that the surface tension decreases approximately the same as the corrosion rate of RI at 400 mg/L.
with the increasing concentration of RI. The surface tension of the Notably, above 10 mg/L TU, the weight loss measurement results
test solution without inhibitor is 77.0 mN/m, which is higher than shows that the corrosion rate increases slightly with a further in-
that in the presence of RI, meaning that RI shows a good surface crease in the concentration. It was reported in previous studies,
activity. It is worth noting that when the concentration of RI ex- this phenomenon could be attributed to the particularly narrow
ceeds 200 mg/L, the decrease in surface tension is negligible, indi- inhibition concentration range of TU. At higher concentration, TU
cating that is the critical micelle concentration is present at around gradually losts its inhibition effect due to formation of soluble
200 mg/L [39]. thiourea complex with metal ions [43,44].

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S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

Table 4
Fitted parameters of the polarization curves for specimens in test solution with different concentration of RI/TU at 80 °C.

RI/TU Concentration (mg/L) ba (mV•dec−1 ) bc (mV•dec−1 ) Ecorr (V vs.Ag/AgCl) icorr (A/cm2 ) Rp (•cm2 ) V (mm•a − 1
) ηP %
Blank 44.56 −200.37 −0.66 1.02 × 10−4 112.6 1.200 —
50/0 84.21 −143.51 −0.61 1.93 × 10−5 973.2 0.22 81.1
100/0 71.89 −105.05 −0.57 8.39 × 10−6 1821.4 0.098 91.8
200/0 63.53 −76.14 −0.58 2.64 × 10−6 4578.1 0.031 97.4
400/0 66.25 −59.46 −0.58 1.10 × 10−6 9703.5 0.012 98.9
200/10 31.73 −135.08 −0.62 1.93 × 10−6 8049.8 0.023 98.1
200/20 24.47 −113.05 −0.62 7.54 × 10−7 26,547 0.009 99.3
200/40 28.67 −83.37 −0.62 6.21 × 10−7 24,152 0.007 99.4
200/80 26.95 −81.65 −0.62 5.59 × 10−7 24,367 0.006 99.5

Fig. 8. SEM image of surface morphology of specimen in test solution at 80 °C: (a) blank solution, (b) 50 mg/L RI, (c) 200 mg/L RI, (d) 400 mg/L RI, (e) 200 mg/L RI +40 mg/L
TU and (f) 200 mg/L RI +80mg/L TU.

Table 5 When RI is used alone, considering the characteristics of

Binding energies of N 1s with 200 mg/L RI or
impedance spectra, the equivalent circuit model shown in Fig. 6c
200 mg/L of RI+40 mg/L of TU.
used to fit the EIS data, which consists of the resistance of so-
Element Components Position (eV) lution (Rs ), the resistance of the layer formed by corrosion prod-
N 1s C=N 399.6 ucts (Rf ), the resistance of charge transfer (Rct ), the capacitance
N-Fe 400.0 of constant phase element of surface film (CPE1 ) and the capac-
itance of constant phase element of electric double layer (CPE2 ).
Under all conditions, the Bod plots exhibit two time constants in
the solution without or with RI which correspond to the high-
frequency capacitive loop, intermediate-frequency capacitive loop,
3.4. EIS measurements respectively. When TU is used synergistically with RI, the equiva-
lent circuit model shown in Fig. 6d used to fit the EIS data, which
Fig. 6 shows the EIS data of samples after 1 h immersion in consists of the resistance of solution (Rs ), the resistance of charge
solutions with different concentrations of RI/TU. It can be found transfer (Rct ), the capacitance of constant phase element of electric
that in each case the Nyquist diagram presents a depressed ca- double layer (CPE1 ), the resistance (RL ), the inductance (L).
pacitive loop, which may be caused by the inhomogeneity of the The fitted parameters are listed in Table 3. In addition, the in-
electrode surface [45]. As shown in Fig. 5a, with an increase in hibition efficiency based on impedance fitting data was calculated
the concentration of RI, the radius of the capacitive loop increases, according to Eq. (5) [46]:
which means that the charge transfer process is hindered by the
Rct − R0ct
inhibitors. RI inhibit metal corrosion by controlling charge trans- η= × 100% (5)
fer resistance and form an adsorption film on the surface of steel Rct
instead of water molecules. Fig. 5b shows the variation of the where Rct and R0ct are the resistance of charge transfer in solution
Nyquist plot with concentration of TU in the solution with 200 mg/ with and without inhibitors, respectively.
L RI. The addition of TU dramatically increases the size of the The value of Rct that could represent the corrosion resistance
capacitor loop, demonstrating that TU could successfully improve varies with inhibitors concentrations. As can be seen from Table 3,
the inhibition performance. In addition, there is no change in the Rct is 67.5  · cm2 in blank solution and it increases with the
shape of the impedance spectra with the addition of RI/TU that the increasing concentration of RI. At 200 mg/L and 400 mg/L, Rct is
presence of the inhibitor has no influence on the corrosion mech- 3654.0  · cm2 and 10,260.2  · cm2 , respectively, and the cor-
anism. responding corrosion inhibition efficiency reaches 98.2% and 99.3%.

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S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

Fig. 9. Cross-sectional SEM micrographs specimens in test solution at 80 °C: (a) blank solution, (b) 50 mg/L RI, (c) 200 mg/L RI, (d) 400 mg/L RI, (e) 200 mg/L RI + 40 mg/L
TU and (f) 200 mg/L RI + 80 mg/L TU.

Table 6 From the Fig. 7a and Table 4, the anodic processes of electrode
Elements ratio of steel surface based on XPS test.
corrosion was significantly inhibited after the addition of RI. It can
Inhibitors C (%) O (%) N (%) Fe (%) S (%) also be seen that the polarization curve shifts sharply in the di-
RI 79.36 15.28 4.63 0.73 0 rection where the current density becomes smaller with the in-
RI+TU 73.71 17.34 4.95 3.59 0.41 crease of concentration of RI. For instance, in the blank solution
the corrosion current density is 1.02 × 10−4 A/cm2 , whereas af-
ter adding 200 mg/L or 400 mg/L RI, the current densities are
This confirms that the addition of RI enhances the corrosion re- 2.64 × 10−6 A/cm2 and 1.10 × 10−6 A/cm2 , respectively. Accord-
sistance of specimen. In addition, at 200 mg/L RI, the addition of ing to the shape of the polarization curves, the ba is much bigger
TU further increases Rct , suggesting that the protective film on the than the blank sample, therefore, it is easy to know that the anodic
specimen surface becomes denser. At 200 mg/ L RI, the concen- reaction is greatly inhibited, and Ecorr of the blank sample is lower
tration of additional TU is 80 mg/L, Rct reaches 20,530.0  · cm2 than that with RI at each concentration. This means that RI has
which is 5.6 times higher than that without TU. The increased an excellent corrosion inhibition and mainly inhibits the anodic
value of Rct and the decreased value of Y02 mean thickening of the reaction.
double-layer capacitance [47,48]. It also indicated that the corro- The polarization curve in solution with 200 mg/L RI plus dif-
sion inhibitors mainly control the charge transfer process which ferent concentrations of TU is show in Fig. 7b. It can be clearly
change electrode surface condition to protect the steel. Simultane- seen that the cathodic reaction is further suppressed after TU is
ously, Rf is roughly the same under all conditions, and this value is additionally added. Compared with RI alone, the Ecorr decreased
very small, indicating that the corrosion product film is extremely when TU was added, indicating that TU inhibited the cathode re-
limited in inhibiting corrosion. It should be noted that, when TU is action and formed a synergistic effect with RI. As can be seen
used synergistically with RI, the variation trend of corrosion inhibi- from Table 4, the significant change occurred in the corrosion cur-
tion efficiency with concentration is different from that of weight rent density. At 80 mg/L TU, the corrosion current density drops
loss measurement. The time period of the weight loss experiment to 5.59 × 10−7 A/cm2 , which is an extremely low level, corre-
is 168 h, the obtained corrosion rate reflects the average corrosion sponding corrosion inhibition efficiency reaches 99.5%. Compared
rate during this period. However, EIS is measured at 1 h immersion to published compounds [49,50], our tested compound possess ex-
of WE in the test solution, which reflects the transient corrosion cellent corrosion inhibition effect, which reduces the corrosion cur-
rate at 1 h. Therefore, the difference between the weight loss re- rent density to an extremely low level.
sult and the EIS result is acceptable, and both indicate that the use Meanwhile, we calculated the polarization resistance based on
of RI in conjunction with TU increases the inhibition efficiency. the polarization curve, and the data obtained are show in Table 4.
It can be found that the polarization resistance of the blank group
3.5. Polarization curve measurements is only 100  · cm2 , while the polarization resistance increases
significantly after RI is added, indicating that RI is adsorbed on the
The polarization curves are shown in Fig. 7. The related electro- steel surface and thus increases the resistance of steel corrosion. In
chemical parameters obtained by Tafel extrapolation method are addition, when TU and RI are used together, the linear polarization
listed Table 4. Based on the corrosion current density obtained by resistance increases sharply, meaning that the synergistic effect of
the polarization curve, the corrosion inhibition efficiency was cal- TU and RI can inhibit the corrosion of steel more effectively.
culated according to the following formula (6) [46]: Based on the above results, it can be concluded that RI is suc-
cessfully adsorbed on the steel surface forming molecular film. Af-
i0 − i
η= × 100% (6) ter TU is additionally added, forming a denser molecular film than
i0 that only consists of RI. This results in a further decrease in the
where i0 and i are the corrosion current density of carbon steel in corrosion current density, thereby the sample is better protected.
the absence and presence of inhibitor, respectively. These results match EIS data well.

8
S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

3.6. SEM analysis

SEM was used to observe the surface morphology of steel af-

ter being exposed to the solution. Fig. 8 shows the surface mor-
phology of samples after immersed in the solution without or
with different concentrations of RI/TU. It is observed that from
Fig. 8a, the steel surface is severely corroded in the blank solu-
tion. Many corrosion products accumulated on the surface. Unfor-
tunately, the accumulation of corrosion products is fractured and
therefore does not hinder further corrosion. As shown in Fig. 8b,
at 50 mg/L RI, corrosion on the steel surface is greatly alleviated,
and scratches produced during the grinding process on the steel
surface could still be observed. However, there are local corrosion
pits on the steel surface, showing that RI of this concentration is
not enough to fully protect the steel surface. With the RI concen-
tration further increases to 200 mg/L and 400 mg/L, as shown in
Fig. 8c,d, the surface morphology of the specimen is smooth and
intact, indicating well protection. The surface morphologies of the
specimen after being exposed to in the test solution with RI in
conjunction with TU are also shown in Fig. 8. With the addition
of TU, the surface morphology of the steel is smoother, and the
scratches of grinding are clearer, showing an excellent protective
effect.
Fig. 9 shows the cross-sectional morphologies of the speci-
mens under different corrosion conditions. As shown in Fig. 9a,
a thick layer of corrosion products can be observed after spec-
imens immersed in blank solution, indicating that the sample
has been severely corroded. Simultaneously, the thickness of the
corrosion product film is not uniform, implying that the film is
loose and easy to peel off. With the addition of RI, the thick-
ness of corrosion product layer becomes thinner. When the con-
centration of RI is 50 mg/L, the thickness of the corrosion prod-
uct film is reduced to about half of that in the blank solution,
which proves the effectiveness of RI as a corrosion inhibitor. At
20 0 mg/L and 40 0 mg/L RI, the corrosion product film thickness
is further thinned. Especially at 400 mg/L, hardly any corrosion
products were observed, indicating that the metal is well protected
by RI. Fig. 9e,f shows the cross-sectional morphology of the speci-
men when RI and TU are used together. Only a trace of corrosion
products is found, indicating that TU enhances the protective effect
of RI on the steel surface. The results of the cross-section analy-
sis are consistent with that of the surface the surface morphology
analysis.

3.7. XPS analysis

XPS tests were further performed to verify corrosion inhibitor

adsorption on the steel surface. The full XPS spectra of the speci-
men surface are shown in Fig. 10a. The presence of N and S peaks
demonstrates the adsorption of RI and TU on the steel surface, re-
spectively. Fig. 10b,c shows the high-resolution spectra of the N 1s
and S 2p. Under both corrosion conditions, the spectra of N 1s is
deconvolved into two peaks. The binding energies for each peak
component are listed in Table 5. The peak at about 399.6 eV is at-
tributed to C = N derived from RI [51], and the peak at 400.0 eV
is due to N-Fe formed on the steel surface [52], which provides
an evidence of the interaction between the N atom and Fe atom.
The high-resolution spectra of S element are not detected in the
solution with only RI. After the addition of TU, the spectra of S
2p is shown in Fig. 10c, and both peaks are derived from TU.
Table 6 shows the ratio of elements on the specimen surface based
on the XPS test results. The proportions of elements in both condi- Fig. 10. (a) Full XPS spectra. XPS high-resolution spectra of (b) N 1s and (c) S 2p of
samples being immersion in solution coating 200 mg/L RI or 200 mg/L RI with an
tions are similar. The presence of C elements may be related to the
additional 40 mg/L TU.
rosin groups in RI. The O element may be caused by ferrous car-
bonate and the inevitable oxidation of the sample in the air after
the samples taken out from test solution.

9
S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

Fig. 11. (a) The optimized geometric structure, (b) HOMO−1, (c) HOMO, (d) LUMO, (e) LUMO+1 and (f) molecular electrostatic potential (MEP) of RI.

3.8. Quantum chemical calculations found that the LUMO are mainly distribute on imidazoline rings,
indicating that imidazoline rings are another possible site for RI
According to the frontier orbital theory, molecular orbital can interacts with Fe atoms. In addition, further analysis for HOMO-1
explain the electron transfer behavior of the corrosion inhibitor reveals that the amino side chain of RI is also a possible adsorption
molecules. The optimized geometric structure, HOMO, HOMO-1, site, and these sites may also provide electron interaction with Fe
LUMO, LUMO+1 of the RI are displayed in Fig. 11. The HOMO and atoms.
LUMO are most often used to analyze the characteristics of cor- The analysis of molecular electrostatic potential can further pre-
rosion inhibitor molecules because of the HOMO and the LUMO dict the active region of the corrosion inhibitor molecule. The MEP
are associated with electron-donating and electron-accepting abil- of the RI is shown in Fig. 11f. As indicated by the color scale bar in
ities of inhibitor molecules, respectively. Considering that RI con- the figure, red and blue represent the most positive and negative
tains multiple ring structures (the imidazoline ring and the tri- positions, respectively. This imply that blue area represents a nu-
cyclic phenanthrene skeleton), more molecular orbitals need to be cleophile attack, while the red area represents an electrophilic at-
studied to analyze the reactive locations of molecules. Because the tack. As can be seen from the picture, the blue region distributes in
HOMO-1 is second only to HOMO in electron-donating ability, and two locations, i.e. the tricyclic phenanthrene skeleton, and the N11
LUMO+1 is second only to LUMO in electron-accepting ability, the atom, indicating that these atoms can be used as sites for nucle-
HOMO-1 and LUMO+1 orbitals have also been studied in this work ophilic attack of RI. This proves that imidazoline synthesized from
[53,54]. rosin has multiple adsorption sites, which meets the original de-
As shown in Fig. 11c, the HOMO of RI mainly distributes on the sign goal using rosin as raw material. Further, the red regions are
conjugated double bonds contained in the tricyclic phenanthrene mainly distributed in N7 and N8 atoms of the imidazoline ring,
skeleton, namely, on the C1, C2, C3 and C4 atoms, which indicates indicating that those atoms tend to experience electrophilic reac-
that these atoms are highly likely to donate electrons Fe atoms. tions, thus they can accept electrons from Fe atoms and then en-
The LUMO+1 are located at the same sites as HOMO, suggesting hance the adsorption of RI on the surface of specimen.
that these sites also possess the ability to accept electrons, but it To further verity the above conclusion, we also calculate the
is relatively weak. It indicates that rosin as a raw material for im- condensed Fukui function. The calculated results are presented in
idazoline synthesis has successfully introduced a new adsorption Fig. 12 in the form of isosurface. The C1, C2, C3 and C4 atom on
site. The distribution of the LUMO are shown in Fig. 11d. It can be the tricyclic phenanthrene skeleton have a relatively high f + value,

10
S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

Fig. 12. The isosurface distribution map of (a) f + and (b) f − values of RI calculated by the condensed Fukui function.

Fig. 13. (a) The optimized geometric structure, (b) HOMO, (c) LUMO for the TU.

meaning that those atoms are the most likely to receive the elec-
trons from Fe atom. The larger f − value is distributed in three
locations, i.e. the C1 and C2 atoms in the tricyclic phenanthrene
skeleton, the N7 and N8 atoms in the imidazoline ring, and N10
and N11 atoms, indicating that these locations are the most likely
to provide electrons to the Fe atoms on the surface of the car-
bon steel. These results are consistent with the frontier orbital and
molecular electrostatic potential analysis, namely, the RI molecules
have multiple active sites for adsorption on the steel surface.
In addition, the molecular parameters of TU are also calculated,
and the optimized geometric structure, HOMO and LUMO of dis-
tribution are shown in Fig. 13. As can be seen that the optimized
TU molecular structure is planar, which means that when TU and
RI molecules are used in collaboration, the TU molecule has the
advantage of adsorption in the molecular film void formed by RI
molecules. The HOMO of TU is mainly occupied by S atom, indi-
cating that the S atom are the most likely to donete electron to
Fe atom. On the other hand, the LUMO of TU is distributed on al-
most all atoms, indicating that the any atoms of TU molecular can
receive electrons, which is a great advantage for TU molecular ad-
sorption on steel surface. Fig. 14. Langmuir adsorption plots for carbon steel in test solution with different
concentrations of RI.
3.9. The inhibition mechanisms of RI
where C denotes the concentration of RI, Kads is the adsorp-
In general, organic corrosion inhibitors are considered to in- tion equilibrium constant, θ is the surface coverage, which is re-
hibit corrosion via adsorption on the metal surface, and the ex- placed by the corrosion inhibition efficiency (η) obtained from
perimental results also indicate that RI as a corrosion inhibitor the weightlessness experiment. In addition, the standard Gibbs
conforms to this theory. To study the adsorption pattern of RI on free energy of adsorption (G0ads ) was calculated by the following
the metal surface in the test solution, different types of adsorp- Eq. (8) [56]:
tion isotherm were tried. It is found that the classical Langmuir  
adsorption isotherm is the best option to describe the adsorption G0ads = −RT ln 1 × 106 Kads (8)
behavior of RI. where R is the universal gas constant, T is the Kelvin tempera-
The Langmuir isotherm can be expressed by the Eq. (7) [55] ture (K), 1 × 106 denotes the concentration of water (mg/L). It is
C 1 clear from Fig. 14 that the plot of C/θ against C exhibits a straight
= +C (7)
θ Kads line. This proves that the adsorption behavior of RI conforms to the

11
S. Geng, J. Hu, J. Yu et al. Journal of Molecular Structure 1250 (2022) 131778

Table 7 (2) The adsorption of RI on steel surface in test solution follows

Thermodynamic parameters of adsorption for
Langmuir adsorption mode. RI exhibits a mixed adsorption type
carbon steel in test solution at 80 °C.
including physical and chemical adsorption, at which chemical
Inhibitors Kads (L/mg) G0ads (kJ/mol ) adsorption is dominant.
RI 0.1324 −34.6285 (3) From the SEM and Electrochemical measurement results, RI is
an excellent corrosion inhibitor, which mainly inhibits the an-
ode reaction. When it is used in conjunction with TU, the cor-
Langmuir adsorption model is reasonable. Based on the basic hy- rosion inhibition performance is further improved. This can at-
potheses of Langmuir adsorption model, it can be inferred that a tributed to that TU attaches to the void of the molecular film
monolayer adsorption film formed by RI on the metal surface [57]. formed by RI, forming a more compact molecular film.
The calculated values of Kads and G0ads are listed in Table 7.
Declaration of Competing Interest
The G0ads of RI is –34.6285 kJ/mol. It is generally believed
that G0ads ≥ −20 kJ/mol indicates a physisorption of the corrosion
The authors declare that there are no conflicts of interest. The
inhibitor, while G0ads ≤ −40 kJ/mol, suggesting a chemisorption authors declare that they have no known competing financial in-
mechanism [58]. Under test conditions, RI exhibits a mixed type of terests or personal relationships that could have appeared to influ-
adsorption including physical and chemical adsorption. As G0ads is ence the work reported in this paper.
close to -40 kJ/mol, chemisorption is dominant. It is well known
that the more negative the value of G0ads , the more strongly the
CRediT authorship contribution statement
corrosion inhibitor adheres to the metal surface. The G0ads value
of RI is relatively negative, so RI strongly adsorbs on the metal sur- Shuai Geng: Methodology, Investigation, Writing – original
face. draft. Junying Hu: Investigation, Writing – review & editing,
Based on the above results obtained from experiments and the- Funding acquisition. Jiansheng Yu: Investigation, Visualization.
oretical calculations results, the corrosion inhibition mechanism of Chenfeng Zhang: Methodology, Validation. Heng Wang: Method-
RI and synergy with TU can be proposed. The corrosion inhibition ology, Validation. Xiankang Zhong: Writing – review & editing,
process under the research conditions can be explained by the ad- Funding acquisition, Supervision.
sorption of RI and TU on the carbon steel surface. The RI molecules
form a molecular film on the steel surface, which hinders the re-
Acknowledgments
action between the aggressive ions in solution and the steel sur-
face. Considering the characteristics of multiple adsorption sites of
Authors are grateful to the support from the National Natu-
RI molecule, it is impossible to consider its adsorption on metal
ral Science Foundation of China (Grant No. 51501160) and Scien-
surface as a single mode. Firstly, the N atoms in the RI molecules
tific and Technological Innovation Team for the Safety of Petroleum
might be protonated in the test solution saturated with CO2 . Pre-
Tubular Goods at Southwest Petroleum University (Grant No.
vious studies have shown that the steel surfaces in acidic solutions
2018CXTD01).
are positively charged [59,60]. Therefore, during the early stages
of adsorption process, the protonated RI is highly likely to be ad- References
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